GB2061994A - Dye-containing liquid crystal compositions - Google Patents
Dye-containing liquid crystal compositions Download PDFInfo
- Publication number
- GB2061994A GB2061994A GB8026521A GB8026521A GB2061994A GB 2061994 A GB2061994 A GB 2061994A GB 8026521 A GB8026521 A GB 8026521A GB 8026521 A GB8026521 A GB 8026521A GB 2061994 A GB2061994 A GB 2061994A
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- GB
- United Kingdom
- Prior art keywords
- anthraquinone
- composition
- formula
- dye
- group
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000975 dye Substances 0.000 claims description 18
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000001000 anthraquinone dye Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- -1 anthraquinone compound Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 230000003098 cholesteric effect Effects 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- SDICTISQCKLMEB-UHFFFAOYSA-N 1,4-diamino-5-nitroanthracene-9,10-dione Chemical compound O=C1C=2C(N)=CC=C(N)C=2C(=O)C2=C1C=CC=C2[N+]([O-])=O SDICTISQCKLMEB-UHFFFAOYSA-N 0.000 claims 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 claims 1
- AQXYVFBSOOBBQV-UHFFFAOYSA-N 1-amino-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2N AQXYVFBSOOBBQV-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004150 EU approved colour Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- KIJUYOHUDBTXOU-UHFFFAOYSA-N 1,5-diamino-2-(4-butoxyphenyl)-4,8-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(OCCCC)=CC=C1C1=CC(O)=C(C(=O)C=2C(=C(O)C=CC=2N)C2=O)C2=C1N KIJUYOHUDBTXOU-UHFFFAOYSA-N 0.000 description 2
- KITDWGXKROZQAP-UHFFFAOYSA-N 2-phenylheptanenitrile Chemical compound CCCCCC(C#N)C1=CC=CC=C1 KITDWGXKROZQAP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- ZNQIAQXHADXXQI-UHFFFAOYSA-N 1-anilino-4-hydroxyanthracene-9,10-dione Chemical class C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(O)=CC=C1NC1=CC=CC=C1 ZNQIAQXHADXXQI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 101100274581 Caenorhabditis elegans chc-1 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101150054854 POU1F1 gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001916 cyano esters Chemical class 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- IIHQNAXFIODVDU-UHFFFAOYSA-N pyrimidine-2-carbonitrile Chemical class N#CC1=NC=CC=N1 IIHQNAXFIODVDU-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
- C09K19/603—Anthroquinonic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Description
1 GB 2 061 994 A 1
SPECIFICATION composition based on liquid crystal for electro-optical device
The invention relates to liquid-crystal-based compositions for use in electro-optical devices and more particularly in display arrangements.
For a dye to be used appropriately in solution in a liquid crystal or a display arrangement, it must: 5 (a) be sufficiently soluble in the liquid crystal; (b) be perfectly stable both chemically (in particular, inert relative to the liquid crystal) and above all photochemically (c) have sufficient intensity of absorption; and (d) not contain any ionic or ionisable groups.
Furthermore, such a dye must have a high order parameter "S" - this parameter corresponding to the measure of the power of orientation of the dye by the molecules of the liquid crystal - for a display with a strong contrast to be obtained. Finally, the basic structure of the compounds envisaged must of course correspond to a colour appropriate for use in a display arrangement, preferably blue and red.
The first dyes used in liquid crystals were azoic dyes or derivatives thereof, as disclosed particularly by D. L. White and G. N. Taylor, J. Appl. Phys. 45, 4718 (1974), by A. Bloom et al., Mol.
Cryst. Liq. Cryst. Letters 41, 1 (1977) and by J. Constant et al., Elec. Letters, 12, 514 (1976). These compounds generally have a relatively high order parameter. On the other hand, most of them do not have an appropriate maximum absorption wavelength, and in particular azoic dyes are not sufficiently 20 stable to light, so they cannot be considered for use in manufacturing commercial liquid-crystal displays.
Research has therefore been carried out leading to the discovery of colouring agents with better stability relative to light. B.D.H. Chemicals Limited, for example, in published European Patent Application No 78300487.2,' have disclosed the fact that some classes of anthraquinones have a better combination of the desired properties mentioned above. These classes are more particularly the 1 -p substituted anilino-4-hydroxy-anthraquinones and the 1,5-di(p-substituted anilino)-anthraquiriones.
Although the above mentioned anthraquinone compounds brought a substantial improvement over azoic compounds as colouring agents for liquid crystals, investigations have nevertheless continued into similar anthraquinone structures in an attempt to find other classes of compounds capable of giving still better combinations of the properties required for use in liquid- crystal display arrangements.
The invention is based inter alia on the discQvery that basic anthraquinone structures, with an NH2 or OH group in position 1, have a higher order parameter when a side chain is substituted on the anthraquinone ring in position 2 or positions 2 and 6, or respectively in position 3 or positions 3 and 7.
The present invention provides a composition based on liquid crystal and designed for use in an electro-optical device, particularly a display arrangement, and containing as pleochroic dye an 35 anthraquinone compound represented by general formula (1) R4 0 R, Y 1 1 X R3 0 R2 Rn where R1 is a substituted or unsubstituted amino group or a hydroxy group; each of R2, R. and R4, which are identical or different, is a hydrogen atom, a substituted or unsubstituted amino group, a hydroxy group or a nitro group; R is a hydrogen or halogen atom ora hydroxy, lower alkyl or lower alkoxy group; 40 n is 1, 2, 3 or 4, the Rs being identical or different when n is 2, 3 or 4; X is a hydrogen or halogen atom, a hydroxy or mercapto group, a straight, branched or cyclic Cl-16 alkyl radical, a substituted or unsubstituted aryl group or a group of formula OR', 0Ar, SIR, COOR', CO0Ar, COO-CM-R', COM, OOCAr, 0OC-C^-R, CONHR', CONHAr, NHR', NHAr, NIHICOR', NHCOAr, OCOOR', 0CO0Ar, CH=N-C,,H4-R, N=CH-C,^-R', N=N-C,HC-R'or N = N-C61-11.-Rl 0 where R' is a hydrogen atom or a straight, branched or cyclic C,-, alkyl residue, and Y is a hydrogen atom or a side chain of the formula:
2 GB 2 061 994 A 2 W' no where X, W' and n' have the same definitions as and are respectively identical to or different from X, R and n, the side chain being in position 6 when the compound is substituted in position 2 and in position 7 when it is substituted in position 3. 5 Such compounds have a good stability to light. Some examples of basic anthraquinone structures are the structures of formula (11), each corresponding to a basic shade of colour, R4 0 R, 1 1 R3 U R2 where RJ, R2, R3 and R4 are as defined above and combined as set out in Table 1 below.
ABLE 1 Basic anthraquinone structures of formula (11) Formula (11) R, R2 R, R4 A NH2 NH2 H H B NH2 H NH2 H c NH2 NH2 NH2 NH2 D NH2 OH H H E NH2 OH OH NH2 F NI-12 OH NH2 OH G NH2 NH2 N02 H H NH2 H H H 1 NH2 H H N11-12 j OH H H H K OH OH H H L OH H OH H m OH H H OH N OH NH2 NH2 OH 0 NH2 H N02 H Colour blue yellow blue red blue blue blue yellow orange yellow orange yellow yellow blue orange The introduction of a side chain in the basic formula (11) structures, in position 2 or positions 2 and 6, or respectively in position 3 or positions 3 and 7, leads to the formula (1) compounds and is designed to increase the order parameter of these basic structures, while maintaining the other properties such a.,
1 3 GB 2 061 994 A 3 chemical stability and stability relative to light, while allowing for the fact that the nature of the side chain influences the shade of colour of the basic structure, the solubility of the structure and the order parameter.
Although a formula (1) dye with a side chain in position 2 (or still better, two side chains), of the alkoxyphenyl type, has a good order parameter in a mixture of liquid crystals based on biphenyi, phenyl cyclohexa ne or pyrimidine, it is not the same with a mixture based on esters. One will then use colouring agents of formula (1) in which the side chain is an ester of benzoic acid. In some compositions it is preferable to use a formula (1) compound with only one side chain rather than two.
Swiss Patent (Application No 8863/79 of 10.2.1979) describes a class of very stable anthraquinone compounds where the order parameter is approximately 0.60 to 0.65. They comprise th( 10 same basic structure of formula (11) as mentioned above, substituted in position 2 or 3 by a side chain similar to that defined for the composition of formula (1) of the present invention, except that the side chain is joined to the anthraquinone ring through the agency of an oxygen atom. Examination of the molecular model of such a compound shows that the angle of 1201 formed by the two bonds of the oxygen bridge does not allow the molecule to take on an ideal elongated shape (see diagram below). 15 This is reflected in the values of the order parameter in the liquid crystal, which are relatively low.
0 0 On the other hand, in the formula (1) compounds used in the composition according to the invention, e.g. compound (1a) below, elimination of the oxygen bridge gives a more rigid, elongated 20 molecule and better conjugation between the lateral substituent and the anthraquinone ring.
X CR4 0 IR, 1 R A n R3 0 R2 For example, for an identical basic anthraquinone structure of formula (11) and for an identical side chain in position 2, the absence of the oxygen bridge enables the order parameter to be increased from 0.60-0.65 to 0.65-0.70. The stability of the compound without any -0- bridge is not substantially different from that with such an -0- bridge, and yet is perfectly adequate for use in 25 solution in a liquid crystal for a display arrangement; this stability is in any case far greater than that of other types of colouring agents with a comparable order parameter.
As far as the length of the side chain or chains is concerned, this at least partly determines the solubility of the formula (1) compound and should consequently not be more than about 24 carbon atoms. Substituents X and R, or respectively X' and R",,,, of the benzene ring present in the side chain 30 or chains each preferably have a maximum of 10 carbon atoms, but when several of these groups are present simultaneously the total number of carbon atoms should not theoretically exceed about 24.
Above this figure there is a probability that compound (1) may not be sufficiently soluble in the liquid crystal and could consequently not be used to colour it.
The invention will now be illustrated with examples in which the properties of some formula (1) 35 compounds have been studied. More particularly, the solubility and order parameter of the compounds mentioned in Table 11 below have been measured, using the following known methods:
Measurement of solubility (by colorimetry) A saturated solution of each of compounds 1 to 19 is prepared in a liquid crystal, and the solution obtained is filtered, 100 g] of the filtrate is taken out and dissolved in 50 cc of chloroform.
The optical density of each solution is measured spectroscopically, and the concentration of the dye at saturation is deducted from the reading, the coefficient of absorption being known in chloroform.
The results obtained are set out in Table 11. In connection with the values given for solubility, it should be pointed out that the solutions were considered as saturated when they contained grains of colouring agent after being heated in isotropic phase and agitated for 3 minutes.
4 GB 2 061 994 A Determination of orderparameter (S) A 0.5% solution of each of compounds 1 to 19 in a liquid crystal is placed in a glass cell 30 11 thick, coated with an aligning film (tangentially evaporated SiO. or polished polyimide). The optical density of each of the solutions is then measured at its maximum absorption in polarised light, firstly when the direction of the polariser is parallel with (pit) and secondly when it is perpendicular to (D-L) 5 the direction of alignment. The order parameter is calculated from the following equation:
S = r-1 r+2 where r is the dichroic ratio corresponding to the ratio pit 1 D i The results obtained have also been set out in Table 11 below. It will be seen from Table 11 that the values10 of the order parmeter (S) varies according to the liquid crystal used for the measurement. In the case of compound No. 14, the order parameter passes from 0.72 measured in '17(temperature of nematicisotropic transition = 59.8IC) to 0.77 measured in---ROTN404- (temperature of nematic-isotropic transition = 105113).
al TABLE 11
Properties of formula (1) compounds Compound 1 (basic structure II-F Side chain(s) Physical Properties Optical Properties Order parameter A, max. rim X position) Y (position) Melting Solubi 1 ity point in S -Ckn CC) LC (%) CHC 1, LC (LC) 595 0.64 580 {595 1 -CH4-0H (2) H >300 2.5 640 0.65 618 0.69 2 -C^-OCH, (2) H 268-270 0.9 580 595 0.65 {618 638 0.70 3 -C6H4-OC3H,, (2) H 225.6-227.5 1.2 5801618 5961640 0.6710.68 4 -C.HI-OC4H9 (2) H 196-198.5 0.4 5801620 5951637 0.6410.66 -C.1rl,.-OCJ-111 (2) H 171-176 4.5 5801618 5961638 0.6410.65 6 -C,^-OC^, (2) H 150-155 6.0 5801618 5981643 0.6510.66 7 -C,,H.,-OC.H,, (2) H 175-181 1.4 5801618 5971642 0.6610.67 8 -C,^-OWC,H, (2) H 181-188 3.8 5801616 5951640 0.6410.65 9 -C,1-14-0OCCH13 (2) H 175.9-180.5 3.5 5821638 5941638 0.6410.66 G) m N 0 T CD (D _th m CF) TABLE 11 (Continued) Properties of formula (1) compounds Compound 1 (basic structure II-F Side chain(s) Physical Properties Optical Properties Order parameter X( max. (nm) X position Y (position) Melting Solubility point in S -QRn (0 C) LC(%) CHClJ LC (LC) -C,H,-OOCC,H,C,H, (2) H 199-203 4.2 5801618 5951640 0.6510.66 11 -C,^0OCCH4OC, H,.(2) H 211-215 4.9 5951616 5951638 0.6410.66 12 -C,,H,OOCC,,H,C.H,, (2) H 170-188 4.5 5801618 5951640 0.6410,65 13 -C,^OC^ (3) -C^OC^ (7) 166-173 7.0 5801618 5961640 0.6810.70 14 -CI)H40C.,H. (3) -C,,H,,-OC,H. (7) 209-215 7.0 5801616 5981640 0.7110. 72 f 3.5 5981640 0.77 -C.H4--OCH, (3) --C,,H4-OCi H,, (7) 210-217 7.2 5801617 5981641 0.7,310. 74' 16 -CM4-OC.H (3) -C,H,,7-OC.H,,, (7) 206 ' 7.5 5791616 5981640 0.7310.75 17 -C,,H4-OC,,H, (2) H 180-184' 4.7 5821640 5961640 0.6510.65 18 -C,,H4--OH (3) H >300 5901634' 0.6710.67 19 -C,^-OCH, (3) H 180-189 5.7 5801614 5981634 0.6810,69 N.B. The liquid crystal (LC) in which the solubility and order parameter are measured is "E7- produced by BIDH Chemicals Limited, except for the values marked with an asterisk (), where the measurements are taken in "iROTN 404" produced by Hoffrnann-La-Roche AG.
1 11 ill 1 c) a) N 0 0) m (0 -Pb 0 1.1 M 0) 7 GB 2 061 994 A 7 As far as the lifetime of the formula (1) anthraquinone dye and hence of the composition of the invention is concerned this depends essentially on the stability of the dye in light. The lifetime is therefore measured as follows for compounds 1 to 19 in Table 11.
A glass cell, similar to that used in determining the order parameter, and containing a solution of each of the above mentioned compounds in a liquid crystal, is subjected to radiation from a "Xenonlamp, filtered so as to reconstitute solar illumination at mid-day in our latitudes (Leyhold Heraeus Sun Test). The thickness of the cell and the concentration of each solution are adjusted to bring the optical density close to 1, and the time taken for the optical density to reach half its initial value is measured. In the case of the formula (1) compounds in Table 11, all have a half life of over 1000 hours. This is perfectly adequate in practice for use as liquid crystal dyes intended for display cells, e.g. for watches or 10 measuring instruments.
The formula (1) compounds which can be used as dyes in solution in liquid crystals for display devices may be prepared by conventional m ethods of synthesising anthraquinone compounds, for example as described by K. Venkataraman et aL, Indian Journal of Chemistry, 9, 1060 (197 1).
The preparation of two formula (1) compounds will now be described by way of example.
Preparation of 4,8diamino- 1,5dihydroxy-3-p-butoxyphenyl-anthraquinone (Compound 4) N H2- 0 OH OH 0 N112 0C4H9 4.0 9 of sodium 4,8-dia mi no- 1, 5-d ihydroxy-a nth raq u inone-2,6-disu Ifonate is dissolved in a mixture of 2.0 g of boric acid and 30 m] concentrated sulphuric acid heated to 801C. The blue solution obtained is cooled to a temperature of 0 to 51C, and 2.8 9 of butoxybenzene is stirred in drop by drop, 20 the colour then changing from blue to reddish brown. The mixture is agitated for a further two hours at 0 to 1 OOC, then poured onto ice. The suspension obtained is heated on reflux for 4 hours to destroy the boric ester, and a violet precipitate is filtered off after cooling, corresponding to 4,8-diamino-1,5 dihydroxy-3-p-butoxyphenyi-a nth raqui none-6-su lphonic acid. The moist precipitate is dissolved hot in a mixture of 24 mi of 33% ammonia and 160 mi of water, and the sulphonic groups are separated by 25 adding 2.2 g of sodium dithionate in stages. The mixture is finally heated to 950C for approximately 2 hours, then cooled and filtered. The precipitate thus obtained is washed with slightly acidified water, then with a great excess of water, and dried. The desired product may further be purified by crystallisation or chromatography if necessary.
Preparation of4,8-diamino-1,5-dihydroxy-2,6-di(p-butoxyphenyl)anthraquinone (Compound 14) 30 NH2 0 OH 1: 0C4H9 H 9C40 OH 0 NH2 8.25 9 of 1, 5-d ihydroxy-4,8-di nitroa nth raq u i none is dissolved in a mixture of 13 g of boric acid and 190 m] of concentrated sulphuric acid. The solution obtained is cooled to from -10 to O'C. 8.50 g of butoxybenzene is added drop by drop and the mixture is kept at the above mentioned temperature for about 1 hour. The reaction mixture is poured onto 200 g of crushed ice, and the resultant suspension is 35 heated at reflux for 4 hours to destroy the boric ester. It is then filtered, washed with water until neutral, and dried. 10 g of the crude product thus obtained is then reduced by heating it to boiling point for 2 hours in a solution containing 50.0 g of sodium sulphide, 250 mi of water and 32 mi of ethanol. The mixture is filtered hot and the precipitate recovered is washed with water until neutral. The moist precipitate is further heated to boiling point with 300 mi of 10% hydrochloric acid, filtered, washed until 40 neutral, and dried. The desired product (compound No. 14) may further be purified by crystallisation or chromatography if necessary.
8 GB 2 061 994 A 8 In the composition according to the invention a single type of liquid crystal may be used, or preferably a mixture of liquid crystals such as those marketed e.g. by BDH Chemicals Limited under references E3, E7, E8 or E9 (the respective compositions being mentioned in published European Patent Application No. 78300487.2) or by Hoffrriann-l-a-roche under references ROTN-1 03 or ROTN 404.
The liquid crystals should preferably be neumatic with positive or negative anisotropy, and may or may 5 not contain an optically active agent in addition.
The composition according to the invention may further comprise two or more formula (1) dyes or possibly other types of anthraquinone dyes, as well as a cholesterising agent and/or an aligning agent.
The cholesterising agent may be the one known from BIDH Chemicals Limited under reference "CB 15-, which is preferably added in a quantity of about 3% of the total composition. The aligning agent designed to disperse the molecules of the liquid crystals perpendicularly to walls of the electro-optical device may be approximately 2% of a surfactant, for example a sorbitol monoester, sorbitol monolaurate being particularly suitable.
Finally, the pleochroic dye of formula (1) is generally present in the composition of the invention in a quantity corresponding to about 0.5 to 5% of the total composition, e.g. preferably about 1.5%.
Some of the commercially available entectic mixtures which are usable as liquid crystals for the realization of a digital display cell, especially for a watch, are mentioned in the following Table Ill. The commercial mixtures of which the reference letter is -E- are provided by B.D.H. Chemicals Ltd. (GB), "TN" by Hoffrnan La-Roche (CH) and "ZLI" by Merck Co. (USA).
TABLE 111
Examples of liquid crystals mixtures Commercial Basic composition TNICC) A6 name o liquid crystals E8 cyano-biphenyls 70.5 + 13 E43 31 84 + 10 TN 103 cyano-esters 81.4 + 25.6 TN 403 cyano-pyrimidines 82.1 + 19.18 TN 404 i-i 105 + 21.36 TN 430 29 69.2 + 17.60 ZLI 1132 phenyl-cyanohexane 70 + 10.3 ZLI 1221 phenyl-cyanohexane + esters 90 + 8.0 ZLI 1344 PCH + esters 90 + 10.8 TNI: temperature of nematic-isotropic transition.
AE: dielectric anisotropy Some examples of compositions according to the invention are mentioned in the following Table W, which allow the realization for example of a watch digital display working at 4.5 V and with a thickness of 8 jum.
The appropriate dye concentration is determined depending on the aimed appearance and taking account of the cell thickness, whereas the cholesterising agent concentration "Cl31 5- is such that the 25 pitch of the induced cholesteric helix corresponds to the used thickness.
9 GB 2 061 994 A 9 TABLE IV
Examples of compositions according to the invention Liquid crystals Dye (1) mixtures TNI CC) (commercial name) (compos.) No. % % "CB15" E8 71.4 14 0.34 4.46 E43 86.2 14 3.42 4.06 TN1 03 88.5 14 0.50 4,80 TN404 106.6 14 0.60 4.98 ZLI 1132 73.7 14 0.03 3.31 E37 94.1 4 0.16 4.20 TN430 72.8 4 1.58 5.27 TN403 84.2 4 0.90 4.83 TN921 103.9 4 0.078 3.54 ZLI 1221 92.8 4 1.56 2.94 ZLI 1344 92.2 4 0.080 3.26 (saturation)
Claims (1)
1. A composition based on liquid crystal and designed for use in an electro-optical device, that contains as pleochroic dye an anthraquinone compound represented by general formula (I):
R4 0 R, Y 1 1 X R3 0 R2 R where R, is a substituted or unsubstituted amino group or a hydroxy group; each of R2, R, arid R, which are identical or different, is a hydrogen atom, a substituted or unsubstituted amino group, a hydroxy group or a nitro group; R is a hydrogen or halogen atom or a hydroxy, lower alkyl or lower alkoxy group; n is 1, 2, 3 or 4, the Rs being identical or different when n is 2, 3 or 4; X is a hydrogen or halogen atom, a hydroxy or mercapto group, a straight, branched or cyclic Cl-'16 alkyl radical, a substituted or unsubstituted 10 aryl group or a group of formula OR', 0Ar, SW, SAr, COOR', CO0Ar, COO-C',Hi-R', OOCRI, OOCAr, OOC- C,H4-R, CONW, CONHAr, NW, NHAr, NHCOR', NHCOAr, OCOOR', 0CO0Ar, CH=N-C,1- 14-W, N=CH-C,1-14-W, N=N-C^-W or N = N-CO, -R' 0 where R' is a hydrogen atom or a straight, branched or cyclic C,, alkyl residue, and Y is a hydrogen 15 atom or a side chain of the formula:
GB 2 061 994 A 10 W' no where X, W' and n' have the same definitions as and are respectively identical to or different from X, R and n, the side chain being in position 6 when the compound is substituted in position 2 and in position 7 when it is substituted in position 3.
2. A composition as claimed in claim 1, in which the anthraquinone dye has the formula:
R4 0 R1 N R3 0 R2 where RJ, R2, R, R4, R, and X are as defined in claim 1.
X Rn 3. A composition as claimed in claim 1, in which the anthraquinone dye has the formula:
R4 0 R, R3 0 R2 X Rn where 111,112, R3, ROR,,anciXareasdefined in claim 1.
4. A composition as claimed in claim 1, in which the anthraquinone dye has the formula:
R4 0 IR, 4 1 0 1 R R3 0 R2 Resn, X R where R1, R2, R3, RI, Rn, R",,,, X and X' are as defined in claim 1.
5. A composition as claimed in claim 1, in which the anthraquincone dye has the formula:
15, R4 0 R, R"nt R3 0 R2 X Rn I.
1 11 GB 2 061 994 A 11 where RV R2, RI, RI, R,, R%', X and X' are as defined in claim 1.
6. A composition as claimed in any one of claims 1 to 5, in which the basic anthraquinone structure substituted in position 2, 2 and 6, 3 or 3 and 7, is 1,4- diamino-anthraquinone, 1,15-diamino anthraquinone, 1-amino-4-hydroxy-anthraquinone, 1,8-dia m ino-4,5- dihydroxy-a nth raq u inone, 1,4 diamino-5-nitro-anthraquinone, 1,4,5,8-tetra mi no-a nthraqui none or 1,5- diamino-4,8-dihydroxy- 5 anthraquinone.
7. A composition as claimed in any one of claims 1 to 6, in which the basic anthraquinone structure is 1, 5-dia m ino-4,13-di hydroxy-a nth raqu inone and the substituent in position 2 or 3 of the anthraquinone ring is -C6H47-0H, -C,,H,47-OCH3, -C6H4-0C?HI' 10 -C6H4--OC4Hg, -C6H4-OCH 11, -C6H4-OC6H131 -C6H4--OC7H15, -C6H4--OCH,7, -C6H4--00CsH l l, -C,H47-OOC,H,3, -C6H400C6H4C4Hg, -C6H40OCC6H4OC,Hl l or C6H40OCC,H4C,H17. 15 8. A composition as claimed in any one of claims 1 to 6, in which the basic anthraquinone structure is 1, 5-dia m i no-4,8-dihyd roxy-a nth raq u inone and the substituents in positions 3 and 7 of the anthraquinone ring are -C,H4-OC3H7, -C,H4-OC4H,, -C6H4--OC,H1, or -C,H4--OC,H,.,. 20 9. A composition as claimed in any one of claims 1 to 8, that comprises one or more neumatic liquid crystals with positive or negative anisotropy.
10. A composition as claimed in claim 9, that comprises an optically active agent that induces a cholesteric structure and/or an aligning agent.
11. A composition as claimed in any preceding claim in the form of a solution of 0.5 to 5% of the 25 anthraquinone dye.
12. A composition as claimed in claim 10 or 11, that comprises approximately 1.5% of a formula (1) anthraquinone dye, approximately 3% of a cholesteric agent and approximately 2% of an aligning agent.
13. A composition as claimed in claim 1, that comprises at least one other anthraquinone dye in 30 accordance with formula (1).
14. A composition as claimed in claim 1, that comprises at least one other anthraquinone dye other than those represented by formula (1).
15. A composition as claimed in claim 1, in which the said compound is any one of those individually specified in Table 11.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981. Published by the Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH754379A CH641828A5 (en) | 1979-08-17 | 1979-08-17 | LIQUID CRYSTAL COMPOSITION FOR ELECTRO-OPTICAL DEVICE. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2061994A true GB2061994A (en) | 1981-05-20 |
| GB2061994B GB2061994B (en) | 1984-08-15 |
Family
ID=4326791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8026521A Expired GB2061994B (en) | 1979-08-17 | 1980-08-14 | Dye-containing liquid crystal compositions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4376715A (en) |
| JP (1) | JPS5632578A (en) |
| CH (1) | CH641828A5 (en) |
| DE (1) | DE3028593C2 (en) |
| FR (1) | FR2463799A1 (en) |
| GB (1) | GB2061994B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482473A (en) * | 1981-10-30 | 1984-11-13 | Alps Electric Co., Ltd. | Liquid crystal mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360447A (en) * | 1979-03-16 | 1982-11-23 | Mitsui Toatsu Chemicals, Inc. | Composition for liquid crystal color display elements |
| US4304683A (en) * | 1979-03-16 | 1981-12-08 | Mitsui Toatsu Chemicals, Inc. | Composition for liquid crystal color display element |
| DE2938132A1 (en) * | 1979-09-20 | 1981-04-09 | Bayer Ag, 5090 Leverkusen | FLUORESCENT DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS LASER DYES |
| CH642393A5 (en) | 1979-10-02 | 1984-04-13 | Ebauches Sa | LIQUID CRYSTAL COMPOSITION FOR ELECTRO-OPTICAL DEVICE. |
| GB2065695B (en) * | 1979-10-12 | 1984-07-25 | Hitachi Ltd | Guest-host type liquid crystal composition and liquid crystal display device using the same |
| JPS56100885A (en) * | 1980-01-17 | 1981-08-13 | Mitsui Toatsu Chem Inc | Composition for liquid crystal color display |
| DE3007198A1 (en) * | 1980-02-26 | 1981-09-03 | Siemens AG, 1000 Berlin und 8000 München | PLEOCHROITIC ANTHRACHINONE DYE, METHOD FOR THE PRODUCTION THEREOF AND USE OF THE DYE |
| DE3014933A1 (en) * | 1980-04-18 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | LIQUID CRYSTAL MATERIALS CONTAINING ANTHRACHINONE DYES |
| EP0043904A3 (en) * | 1980-07-10 | 1982-03-31 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Mixtures containing a dyestuff, dyestuffs and their use in liquid crystal mixtures |
| US4391489A (en) * | 1980-07-29 | 1983-07-05 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal materials containing pleochroic anthraquinone dyes |
| US4405211A (en) * | 1980-07-29 | 1983-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal compositions with pleochroic anthraquinone dyes |
| JPS57501238A (en) * | 1980-07-31 | 1982-07-15 | ||
| JPS5755984A (en) * | 1980-09-22 | 1982-04-03 | Hitachi Ltd | Liquid crystal composition |
| DE3036896A1 (en) * | 1980-09-30 | 1982-04-15 | Siemens AG, 1000 Berlin und 8000 München | LIQUID CRYSTAL MIXTURE WITH A PLEOCHROITIC ANTHRACHINONE DYE AND METHOD FOR PRODUCING SUCH A DYE |
| DE3036895C2 (en) * | 1980-09-30 | 1985-07-11 | Merck Patent Gmbh, 6100 Darmstadt | Anthraquinone pleochroism dye and manufacturing process for such a dye and its use in a liquid crystal mixture |
| DE3040102A1 (en) * | 1980-10-24 | 1982-06-03 | Merck Patent Gmbh, 6100 Darmstadt | DICHROITIC ANTHRACHINONE DYES, THIS CONTAINING LIQUID CRYSTALINE DIELECTRICS AND ELECTRO-OPTICAL DISPLAY ELEMENT |
| DE3046904A1 (en) * | 1980-12-12 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | ANTHRACHINONE DYES, METHOD FOR THE PRODUCTION THEREOF, AND THE USE OF LIQUID CRYSTAL MATERIALS CONTAINING ANTHRACHINONE DYES |
| DE3167759D1 (en) * | 1981-01-10 | 1985-01-24 | Basf Ag | Dyes for liquid crystal mixtures |
| JPS57126879A (en) * | 1981-01-12 | 1982-08-06 | Sumitomo Chem Co Ltd | Liquid crystal display element |
| DE3201120A1 (en) * | 1981-01-17 | 1982-10-21 | Hitachi, Ltd., Tokyo | LIQUID CRYSTAL COMPOSITION |
| JPS57155282A (en) * | 1981-03-20 | 1982-09-25 | Mitsubishi Chem Ind Ltd | Liquid crystal composition |
| DE3126108A1 (en) * | 1981-07-02 | 1983-01-20 | Merck Patent Gmbh, 6100 Darmstadt | "LIQUID CRYSTAL DIELECTRIC, NEW DICHROITIC NAPHTHOQUINONE DYES AND ELECTRO-OPTICAL DISPLAY ELEMENT" |
| JPS5825381A (en) * | 1981-08-08 | 1983-02-15 | Nippon Kanko Shikiso Kenkyusho:Kk | Liquid crystal composition |
| DE3137298A1 (en) * | 1981-09-18 | 1983-04-14 | Bayer Ag, 5090 Leverkusen | ANTHRACHINONE DYES |
| JPS58109579A (en) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | Color liquid crystal display element |
| JPS58109580A (en) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | Color liquid crystal display element |
| JPS58109578A (en) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | Color liquid crystal display element |
| JPS58111882A (en) * | 1981-12-25 | 1983-07-04 | Alps Electric Co Ltd | Color liquid crystal display device |
| DE3202761A1 (en) * | 1982-01-28 | 1983-08-04 | Merck Patent Gmbh, 6100 Darmstadt | LIQUID CRYSTAL DIELECTRIC, NEW COLORS, METHOD FOR THEIR PRODUCTION AND ELECTRO-OPTICAL DISPLAY ELEMENT |
| DE3216455A1 (en) * | 1982-05-03 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | ANTHRACHINONE DYES, THEIR PRODUCTION AND USE, AND SEALANT MATERIAL CONTAINING THESE ANTHRACHINONE DYES |
| EP0099014A3 (en) * | 1982-07-16 | 1984-12-12 | Asulab S.A. | Dark coloured composition based on liquid crystals |
| DE3247896A1 (en) * | 1982-12-24 | 1984-06-28 | Merck Patent Gmbh, 6100 Darmstadt | ANTHRACHINONE DYES |
| US4530572A (en) * | 1982-12-30 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Substituted anthraquinone-type isotropic dyes for liquid crystal display devices |
| DE3441937A1 (en) * | 1984-11-16 | 1986-05-28 | Bayer Ag, 5090 Leverkusen | LIQUID CRYSTAL MATERIAL |
| US4808080A (en) * | 1986-07-22 | 1989-02-28 | Electric Power Research Institute | Flow coupler assembly for double-pool-type reactor |
| DE3639156A1 (en) * | 1986-11-15 | 1988-05-26 | Basf Ag | TRISAZO DYES |
| FR2627864A1 (en) * | 1988-02-29 | 1989-09-01 | Asulab Sa | DISPLAY DEVICE FOR MEASURING INSTRUMENT |
| FR2743924B1 (en) | 1996-01-23 | 1998-05-22 | Asulab Sa | DEVICE FOR DISPLAYING A DECOR AND WATCHMAKING PART COMPRISING SAME |
| CN105778928B (en) * | 2011-08-31 | 2018-06-08 | Jsr株式会社 | Manufacturing method, aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display element of liquid crystal display element |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL287697A (en) * | 1962-01-12 | |||
| NL7204838A (en) * | 1971-04-14 | 1972-10-17 | ||
| CH597170A5 (en) * | 1974-12-20 | 1978-03-31 | Ciba Geigy Ag | |
| CH619976A5 (en) * | 1975-12-23 | 1980-10-31 | Ciba Geigy Ag | |
| DE2714768C3 (en) * | 1977-04-02 | 1979-09-13 | Bayer Ag, 5090 Leverkusen | Transfer printing process |
| JPS54134452A (en) * | 1978-04-10 | 1979-10-18 | Hitachi Ltd | Quest-host type liquid crystal display device |
| JPS54157786A (en) * | 1978-05-23 | 1979-12-12 | Minnesota Mining & Mfg | Multiicoloring dyestuff and photoelectric display device |
-
1979
- 1979-08-17 CH CH754379A patent/CH641828A5/en not_active IP Right Cessation
-
1980
- 1980-07-24 FR FR8016622A patent/FR2463799A1/en active Granted
- 1980-07-25 US US06/172,641 patent/US4376715A/en not_active Expired - Lifetime
- 1980-07-28 DE DE3028593A patent/DE3028593C2/en not_active Expired
- 1980-08-13 JP JP11043880A patent/JPS5632578A/en active Pending
- 1980-08-14 GB GB8026521A patent/GB2061994B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482473A (en) * | 1981-10-30 | 1984-11-13 | Alps Electric Co., Ltd. | Liquid crystal mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2463799A1 (en) | 1981-02-27 |
| CH641828A5 (en) | 1984-03-15 |
| US4376715A (en) | 1983-03-15 |
| DE3028593A1 (en) | 1981-02-19 |
| GB2061994B (en) | 1984-08-15 |
| JPS5632578A (en) | 1981-04-02 |
| DE3028593C2 (en) | 1982-11-04 |
| FR2463799B1 (en) | 1984-06-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |